Catalytic adsorbents obtained from municipal sludges, industrial sludges, compost and tobacco waste and process for their production

ABSTRACT

Industrial waste derived adsorbents were obtained by pyrolysis of sewage sludge, metal sludge, waste oil sludge and tobacco waste in some combination. The materials were used as media to remove hydrogen sulfide at room temperature in the presence of moisture. The initial and exhausted adsorbents after the breakthrough tests were characterized using sorption of nitrogen, thermal analysis, XRD, ICP, and surface pH measurements. Mixing tobacco and sludges result in a strong synergy enhancing the catalytic properties of adsorbents. During pyrolysis new mineral phases are formed as a result of solid state reaction between the components of the sludges. High temperature of pyrolysis is beneficial for the adsorbents due to the enhanced activation of carbonaceous phase and chemical stabilization of inorganic phase. Samples obtained at low temperature are sensitive to water, which deactivates their catalytic centers.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application claims priority to U.S. Provisional PatentApplication Nos. 60/715,788 filed Sep. 8, 2005; 60/782,593 filed Mar.14, 2006; and 60/801,545 filed May 17, 2006. The entireties of theapplications are incorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates to the formation of catalytic adsorbents formedfrom the pyrolysis of different types of sludges alone or in combinationwith composting materials. The sludges include municipal, industrial,waste oil and metal based sludges. The composting materials can includetobacco waste.

2. Discussion of the Related Art

Growing concerns about the environment has resulted in the developmentof new environmentally friendly technologies, new materials, and newways to reduce and minimize wastes. One of the wastes produced bycontemporary society in abundant quantity is municipal sewage sludge,often referred to as biosolids. Biosolids are a mixture of exhaustedbiomass generated in the aerobic and anaerobic digestion of the organicconstituents of municipal sewage along with inorganic materials such assand and metal oxides. Other sludges include wastes from such industryas shipyards, foundry, or paper mills. It is estimated that about 10million dry tons of sewage sludge is produced in the United States.Moreover, Sweden alone contributes 220,000 dry tons of sludge to the8-10 million tons of dry sludge produced by European Union.

Various methods have been used to dispose of or utilize municipal sewagesludge, including incineration, landfilling, road surfacing, conversionto fertilizer, compression into building blocks, and carbonization.Since 1976, several patents have been issued on carbonization of sewagesludge and various applications of the final materials. Carbonization ofsludge in the presence of chemical activating agents such as zincchloride and sulfuric acid produces new sorbents, with patentedapplications in processes such as removal of organics in the finalstages of water cleaning and removal of chlorinated organics. Industrialsludges after dewatering processes/drying are ether used as landfills ordisposed mainly as hazardous wastes.

Carbonization of sludge to remove pollutants either from gas of liquidphase, is based on the fact that typically activated carbons are chosen.This is owing to their large surface area and high volume of pores.Often, these characteristics of activated carbons are not potent enoughto retain certain molecules, especially small ones, for which thedispersive interactions with the carbon surface are rather weak. In suchcases, the carbon surface has to be modified to impose the specificinteractions. These interactions include hydrogen bonding, complexation,acid/base reactions or redox processes. Fortunately, in the case ofcarbons, various technologies leading to modified surfaces exist and arerelatively easy to achieve. Examples are oxidations with variousoxidants such as strong acids, ozone, or air, impregnation withcatalytic metals or reducing/oxidizing compounds, heat treatment in thepresence of heteroatom sources such as chlorine or nitrogen compounds,and others.

As a result of the treatments mentioned above, new functionalgroups/chemical species are introduced to the surface. They impose thespecific and/or chemical interactions with the species to be removed. Tohave the removal process efficient, the chemical state of these speciesand their dispersion on the surface are important issues. Anotherimportant challenge is preservation of carbon porosity which is acrucial asset for the retention/storage of pollutants. Thus, the surfacemodifications can be done in such a way in which a minimal decrease inthe surface area/pore occur.

Taking into account the above requirements, in some cases modificationsof a carbon surface, besides being a challenge, can also be associatedwith high expenses, especially when noble or catalytic metals areinvolved. Industrial sludges, as those coming from shipyards or otherheavy metal industries, are rich in catalytic transition metals. Bypyrolysis of these materials, not only the volume of waste is reducedbut those environmentally detrimental wastes can be recycled andconverted into valuable products. These products, when used, can besafely disposed since the leaching of materials is significantly reducedby mineralization of those metals via high temperature solid statereactions.

The process of carbonization of sewage sludges has been studied indetail previously and it is described in the literature. Materialsobtained as a result of the treatment have surface areas between 100 and500 m²/g. Their performance as adsorbents of hydrogen sulfides, sulfurdioxide, basic or acidic dyes, phenol or mercury has been reported ascomparable or better that that of activated carbons. In many process theexcellent sorption ability of these materials is linked to the catalyticaction of metals present in various forms in the final products. Theirchemical forms along with the location on the surface were reported asimportant factors governing the pollutant removal capacities. In somecase the wastes were mingled and, owing to the synergy between thecomponents, more efficient adsorbents were obtained.

Adsorbents obtained by pyrolysis of sludge can be considered as complexpseudocomposite materials. However, the process of carbonization ofbiosolids has been studied in detail previously and it is described inthe literature. It has been recently shown that by simple pyrolysis ofmunicipal sewage sludge derived fertilizer, Terrene®, exceptionally goodadsorbents for removal of sulfur containing gases can be obtained. Theremoval capacity is twice that of coconut shell based activated carbon.Although, it was attributed to the specific combination of inorganicoxides of such metals as iron, copper, zinc or calcium. The predominantinfluence of inorganic phase or combination of oxides, which are alsoquite commonly used as catalysts for hydrogen sulfide oxidation orsulfur dioxide adsorption, was ruled out on the bases of the performanceof a pure inorganic phase in the removal of sulfur containing gases. Thecapacity of pure inorganic phase heated at 950° C. was negligible. Thedata also showed that the oxidation of hydrogen sulfide occurs until allmicropores (mainly about 6 Å in size), likely within carbonaceousdeposit or on the carbon/oxide interface, are filled with the reactionproducts. The form of that carbonaceous deposit is important and thatdeposit may play a role in adsorption capacity.

The products of oxidation immobilized on the surface are stored there.Table 1 shows the capacity of sewage sludge derived materials asadsorbents of sulfur containing gases. For removal of a toxic gascontaining reduced sulfur the capacity is much greater than that ofactivated carbons. It happens in spite of the fact that the carboncontent is small (about 20%) and pore volume much smaller than that ofcarbons. TABLE 1 H₂S and SO₂ breakthrough capacities for sludge derivedadsorbents (SC series) and activated carbon (S208). The number after SCrefers to the temperature of heat treatment in Centigrade. H₂Sbreakthrough capacity SO₂ breakthrough capacity Sample [mg/g] [mg/g]SC-400 8.2 5.1 SC-600 14.9 9.5 SC-800 23.6 22.2 SC-950 82.6 29.8 S20848.8 48.2

Since pore volume seems to be a limiting factor for the capacity ofsewage sludge derived materials, an increase in the content ofcarbonaceous deposit and pore volume with maintaining the desiredcontent of a catalytically active phase seems to be the desireddirection of feature research. Resent studies showed that the porevolume active in the removal of such compounds as hydrogen sulfide doesnot need to be in pores similar in size to adsorbent molecule. Since thecatalytic oxidation is the predominant mechanism of adsorption, thelarger pores, (meso- and macropores) where the product of oxidation isstored were found to be beneficial.

Another important factor is the chemistry of a catalytic phase, itsdispersion, location on the surface, compatibility with the carbon phaseand the effects of both phases on the removal process(adsorption/catalytic oxidation/storage). It was found that excellentcapacity of an expensive desulfurization catalyst, US Filter carbonMidas®, is linked to the presence of calcium and magnesium oxidesdispersed within the microporous activated carbon. On this catalyst,hydrogen sulfide is oxidized on basic centers of alkali earth metaloxides and sulfur is formed. The fact that this carbon is able retain upto 60 wt % sulfur is linked to a limited reactivity of MgO and CaO. Ontheir surface, due to the basic pH and the presence of moisture, sulfuris formed and owing to the close proximity of the carbon phase, thatsulfur migrates to the high-energy adsorption centers, small pores. Inthis way the catalytic centers are renewed and the adsorbents worksuntil all small pores are filled by sulfur.

Sewage sludge based materials were also found as efficient adsorbentsfor removal of mercury from waste water and copper. Other commonindustrial pollutants which can be efficiently removed using thosematerials are basic and acidic dyes. In the case of these adsorbates thehigh capacity is linked to surface chemical nature (acidic and basicsites) and relatively large pores which are similar in size to themolecules of organic dyes.

At high temperature, the organic matter vaporizes, dehydrogenationoccurs and carbon can be deposited back on the surface of an inorganicsupport as carbon nanotubes of filaments. This may happen due to thepresence of highly dispersed catalytically active metals. Since thisprocess resembles the chemical vapor deposition (CVD), it is referred toas the self-imposed chemical vapor deposition (SICVD). The process ofcarbon nanotube growth on the catalysts containing nickel or cobalt iswell-known and described in the literature. The nanotubes and carbonfilaments grow on metal “seeds” and their effective size depends on thesizes of the seeds. Introduction of more carbon phase can increase theporosity leading to more space for storing of oxidation products andalso can lead to the formation of greater quantity of novel carbonentities in the process of CVD. FIG. 1 shows an SEM image of carbonnanotubes grown on the surface of sewage sludge-derived materials.

The carbon and nitrogen content of the sludge plays a role in theformation and properties of the adsorbent. While municipal sewage sludgeis a promising material to use as a base with other waste sludges, othercarbon or nitrogen based wastes can also be used. Besides formation ofnew carbon entities in the presence of catalytic metals as a result ofheat treatment the new spinel-like/mineral like active components can beformed. Recently, for some sewage sludges containing iron and calciumthe catalytically important entities were identified as dicalciumferrite (Ca₂Fe₂O₅).

SUMMARY OF THE INVENTION

Definitions

The term “adsorption” refers to the phenomenon wherein the surface of asolid accumulates a concentration of molecules from its gaseous orliquid environment.

The term “adsorbent” refers to a material that is able to adsorb gasesor vapors under certain conditions.

The term “pyrolysis” refers to heat treatment (e.g., at a temperatureover 400° C.) in inert atmosphere of materials having organic origin.

The term “chemical activation” refers to the treatment of organicprecursors with certain chemicals during pyrolysis.

The term “activated carbon” refers to a carbonaceous material obtainedby pyrolysis of organic precursors (e.g., coal, wood, peat, etc.) atelevated temperatures followed by their activation using variousphysical or chemical agents (e.g., at a temperature between about 600°C. and 1,000° C.).

The term “caustic-impregnated carbon” refers to activated carbonsimpregnated with KOH and NaOH in order to increase their pH andadsorption capacity for acidic gases.

The term “breakthrough capacity” refers to the amount of substanceadsorbed on the sorbent surface until the substance is detected ineffluent air at a certain concentration level.

The term “acidic gases” refers to gases that are able to transform intoacids, or gases that are able to interact as acid (e.g., electronacceptors).

The term “specific surface area” refers to the surface area of adsorbentconsidered as an area where adsorption of various molecules could occur.

The term “pore volume” refers to the volume of pores in an adsorbentcalculated as available for nitrogen molecules at its boiling point.

The term “oxidation” refers to the change in the chemical stage of asubstance associated with an electron loss. The charge on the speciesbecomes more positive.

The term “residence time” refers to the average time taken by reagentmolecules to pass through a reactor.

The term “compost material” refers to the individual materials that arecomposted.

The term “compost” can refer to either a mixture that consists largelyof decayed organic matter or the act of converting compost materialsinto compost.

Waste oil sludge, waste metal sludge (both from a shipyard, but theorigin of the sludges can be from any heavy industry facilities wheretransition metals such as iron, zinc, copper, nickel, chromium are used)were mixed with municipal sewage sludge at different proportions thenpyrolyzed in the nitrogen atmosphere at 650° C. and 950° C. for twodifferent time periods (half an hour and an hour). Additional sampleswere pyrolyzed in the nitrogen atmosphere at a low temperature, e.g.,about 600° C., 625° C., 650° C., 675° C., or 700° C. or less, and at ahigh temperature, e.g., about 900° C., 925° C., 950° C., or 975° C.,1,000° C., 1,100° C. or higher. As used herein, the term “industrialsludge” includes any sludge that is not domestic wastewater sludge. Thisincludes wastewater sludge from manufacturing or processing of rawmaterials, intermediate products, final products or other activitiesthat include pollutants from non-domestic wastewater sources.“Municipal” or “domestic” wastewater sludge can be generated at plantsservicing the general population and may conform to the “10 StateStandards.”

Combinations of compost/compost materials and municipal/industrialsludge, along with pyrolyzation in a nitrogen atmosphere, can lead toformation of new adsorbents. The new adsorbents can consist of aninorganic phase (70-95% and 80-98%) and a carbonaceous phase (5-30% and10-30%). The inorganic phase can contain highly dispersed catalyticmetals such as iron, nickel, copper, zinc, chromium, and calcium andmagnesium oxides, alumina, silica, etc.

As a result of synergy, a ceramics/mineral-like phase is formed. Thisphase reacts with nitrogen gas when exposed to elevated temperatures.The specific surface areas are about 10 m²/g to about 200 m²/g. Forexample, the specific surface areas may be about 10 m²/g, 20 m²/g, 30m²/g, 40 m²/g, 50 m²/g, 60 m²/g, 70 m²/g, 80 m²/g, 90 m²/g, 100 m²/g,110 m²/g, 120 m²/g, 130 m²/g, 140 m²/g, 150 m²/g, 160 m²/g, 170 m²/g,180 m²/g, 190 m²/g, 200 m²/g, or greater. The specific pore volumes areabout 0.002 cm³/g to about 0.074 m²/g. For example, the specific porevolumes are about 0.002 cm³/g, 0.005 m²/g, 0.015 m²/g, 0.025 m²/g, 0.035m²/g, 0.045 m²/g, 0.055 m²/g, 0.065 m²/g, 0.074 m²/g, or greater. Animportant aspect of the texture is a significant volume of mesoporesreaching about 0.8 cm³/g. All materials have basic pH, e.g., a pH over9. They are capable of adsorbing up to about 10, 15, 20, 25, or 30 wt %of hydrogen sulfide, mainly as elemental sulfur.

The discovered solid state reactions form ceramics/mineral likecrystallographic phases. Spinel-like compounds can form whenmunicipal/industrial sludge is pyrolized at 950° C., such as wurtzite(ZnS), ferroan (Ca₂(Mg, Fe)₅(SiAl)₈O₂₂(OH)₂), chalcocite (Cu_(1.96)S),spinel (MgAl₂O₄), and feroxyhite (FeO(OH)) were found. In wasteoil-based materials besides metallic iron, bornite (Cu₅FeS₄), hibonite(CaAl₁₂O₁₉), zincite (ZnO), ankerite (Ca(Fe, Mg)(CO₃)₂) are present. Inmetal sludge based adsorbent aluminum, metallic iron, copper, zinc,pyrope (Mg₃Al₂(SiO₄)₃₎, perrohotite (Fe₇S₈), Chalocopyrite (CuFeS₂),Triolite (FeS) and Fersilicite, (FeSi) exist. Mixing industrial sludgeswith compost or compost materials can result in synergy enhancing thecatalytic properties which can be linked to formation of new entitiessuch as sapphirine (Mg_(3.5)Al₉Si_(1.5)O₂₀), maghemite (Fe₂O₃), cohenite(Fe₃C), lawsonite (CaAl₂Si₂O₇(OH)2H₂O), smithsonite (ZnCO₃), sphalerite(ZnS), and hematite (Fe₂O₃).

The new entities can be formed during pyrolysis that react with nitrogengas when exposed to elevated temperatures (200-600° C.). This can resultin an increase in weight between 0-3%. Some of these entities can benitrides. The specific surface areas and total pore volumes of theadsorbents are between 10-210 m²/g and 0.15-0.85 cm³/g, respectively. Animportant aspect of the texture can be a significant volume of mesoporesreaching 0.8 cm³/g (between 0.14-0.77 cm³/g). All materials have basicpH between 7-12. They are capable to adsorb up to 30 wt % of hydrogensulfide mainly as elemental sulfur. Exposure to hydrogen sulfide anddeposition of sulfur results in an increase in the volume of mesoporesup to 25% as a result of formation of new pore space in-betweendeposited sulfur in large pores. The important components besidesalkaline earth metals and transition metals are iron oxides andhydoxyoxides (but not only) since they contribute to oxidation ofhydrogen sulfide to elemental sulfur. The developed materials are alsogood adsorbents of cationic or ionic dyes and heavy metals (up to 80mg/g copper and up to 130 mg/g dyes). The spinel-like phase formedduring pyrolysis contributes to cation exchange, complexations andprecipitation reactions. During these reactions only small quantity ofcalcium and zinc is released to the solution as a result of a cationexchange process.

The present invention uses the combination of compost and/or compostmaterials and municipal and/or industrial waste sludge to formadsorbents. Successful results used fertilizer and municipal sludge tocreate adsorbents, because they contain, in part, large amounts ofcarbon and nitrogen. Other wastes are available that are rich in carbonand nitrogen to use as a base material. One waste is compost and compostmaterials. Compost materials can be divided into two categories,“brown”—high in carbon, and “green”—high in nitrogen.

Brown compost materials can be fall leaves, spent plants, straw and hay,pine needles, small twigs and wood chips, sawdust and woodshavings,shredded newspaper, egg shells, corncobs, bread and grains, wood ashes,old potting soil, food-soiled paper towels and napkins, dried flowers,brewery waste, hops, and pomace, food-soiled cardboard (recycle ifclean, but compost if dirty), stale flour, cereal, spices, beans,nutshells, meat and fish scraps.

Green compost materials can be fruit and vegetable scraps, coffeegrounds and filters, tea bags, fresh leaves, green plants, prunings andhedge trimmings, grass clippings, weeds, flower bouquets, seaweed,feathers, horse manure, manure and bedding from small pets such ashamsters and rabbits, cornstarch and other organic packing materials,and spoiled juice.

Additionally, over 70,000 tons of tobacco waste is generated every yearduring the production of cigarettes. In India alone, over 20 years ago,almost 100,000 tons of tobacco waste was generated, and more isgenerated every year. Tobacco waste is currently used as a compostmaterial and fertilizer. Tobacco waste spans the entire cigarette makingprocess from growing and harvesting to final production. The types ofwastes generated during pre- and post- harvest practice of tobaccoinclude suckers, stems, mid ribs, leaf waste and dust. For example,green trimmings are generated as the either the stalks and/or leaves areharvested and separated from their stalks for curing. After curing,certain varieties of tobacco are threshed (by separating the midrib ofthe leaf) generating particle waste and stalks can also be removed atthis stage, depending on the type of tobacco. Stems are removed from thecured and aged tobacco and the leaves and stems are chopped and blended.Tobacco dust can be formed during the chopping and blending stages.Further dust can be generated as the chopped tobacco is formed intotobacco rods and finally wrapped into paper. Some chemicalcharacteristics of tobacco waste are listed in Table 2. TABLE 2 SomeChemical Characteristics of Tobacco pH EC(1/5) Ca Mg N K P Na Fe Cu ZnMn O.M. % (1/5) (μm/cm) (μg/g) (μg/g) (%) (%) (μg/g) (μg/g) (μg/g)(μg/g) (μg/g) (μg/g) 41 5.80 10700 8050 9400 2.35 1.95 973 572 3150 8490 279

The use of compost and/or compost material was determined from studiesusing combinations of municipal sewage sludge and industrial sludge andmunicipal sludge and waste paper. The waste paper is used for its highcarbon content. The paper was ground fine and added to the sludge.Compost materials can be ground like the paper and tobacco dust is inparticulate/powder form. Sawdust is another compost material that isalready in particulate/powder form. Sawdust is a brown compost materialthat is high in carbon. Wood char/ash can also be used based on itscarbon content.

The invention can combine the compost/compost materials with industrialsludge or with a mixture of municipal and industrial sludge. Thecompost/compost materials can be wetted as it is mixed, or may containenough natural moisture to be mixed directly. The ratios of compost tosludge can range between 25% and 75%. Additionally, calcium hydroxidemay be added to help influence the dissociation of hydrogen sulfide.

BRIEF DESCRIPTION OF THE FIGURES

The above and still further objects, features and advantages of thepresent invention will become apparent upon consideration of thefollowing detailed description of a specific embodiment thereof,especially when taken in conjunction with the accompanying drawingswherein like reference numerals in the various figures are utilized todesignate like components, and wherein:

FIG. 1 is a SEM image of the carbon nanotubes on the surface of sewagesludge-derived adsorbent of the prior art;

FIGS. 2A and 2B are graphs depicting the predicted and measured volumeof meso- and micro-pores, respectively, for the adsorbents derived frommixtures of industrial and municipal sludges;

FIG. 3 is a graph depicting dependence of H₂S removal capacity on thevolume of mesopores in industrial and municipal sludge-derivedadsorbents;

FIG. 4 is a graph depicting a comparison of the predicted and measuredH₂S breakthrough capacity for sewage and industrial sludge-basedadsorbents;

FIG. 5 is a graph depicting DTG curves in nitrogen for selectedadsorbants for initial and H₂S exposed samples (E);

FIG. 6 is a graph depicting DTG curves in nitrogen for selectedadsorbants for initial and H₂S exposed samples (E);

FIGS. 7A and 7B illustrate X-ray diffraction patterns at 650° C. and950° C., respectively;

FIG. 8 illustrates changes in pore size distribution after H₂Sadsorption;

FIG. 9 illustrates DTG curves in nitrogen for initial and exhaustedsamples;

FIG. 10 shows X-ray diffraction patterns for samples obtained at 650°C.;

FIG. 11 illustrates a comparison of the measured and predicted mesoporesvolume for WOSS samples obtained at various conditions;

FIG. 12 illustrates a comparison of the measured and predicted H₂Sbreakthrough capacities for samples obtained at various conditions;

FIG. 13 illustrates the H₂S breakthrough capacity curves for adsorbentsobtained at 650° C.;

FIG. 14 illustrates the H₂S breakthrough curves for adsorbents obtainedat 950° C.;

FIG. 15 illustrates the dependence of the H₂S breakthrough capacity onthe amount of preadsorbed water;

FIG. 16 illustrates a comparison of measured and calculated (assumingthe physical mixture of components) H₂S breakthrough capacities;

FIG. 17 illustrates XRD patterns for tobacco derived samples;

FIG. 18 illustrates XRD patterns for metal and waste oil sludge derivedadsorbents;

FIG. 19 illustrate a XRD diffraction pattern for composite tobacco/metalsludge based adsorbents;

FIG. 20 illustrates nitrogen adsorption isotherms for samples pyrolyzedat 650° C.;

FIG. 21 illustrates nitrogen adsorption isotherms for samples pyrolyzedat 950° C.;

FIG. 22 illustrates pore size distributions for single componentsamples;

FIGS. 23A and 23B illustrate pore size distributions for samplespyrolyzed at 650° C.;

FIGS. 24A and 24B illustrate pore size distributions for samplespyrolyzed at 950° C.;

FIG. 25 shows a comparison of the volume of micropores measured andcalculated assuming physical mixture of the components;

FIG. 26 shows a comparison of the volume of mesopores measured andcalculated assuming physical mixture of the components;

FIG. 27 illustrates the dependence of H₂S breakthrough capacity on thevolume of pores (micropores and mesopores for samples pyrolyzed at twotemperatures);

FIG. 28 illustrates DTG curves in nitrogen for single component samples;

FIGS. 29A and 29B illustrate DTG curves in nitrogen for samplespyrolyzed at 650° C.; and

FIGS. 30A and 30B illustrate DTG curves in nitrogen for samplespyrolyzed at 950° C.

DETAILED DESCRIPTION OF THE INVENTION

Industrial sludges such as waste oil sludge and metal sludge can beutilized using pyrolysis to produce new catalytic adsorbents. Animportant result of mixing is an enhancement in the properties of theabove-mentioned sewage sludge-based adsorbents. Although only waste oilsludge can lead to adsorbents with an exceptional ability fordesulfurization with 30 wt % removal capacity, the presence of sewagesludge is an economically feasible method of utilizing this abundantmaterial.

Mixing the sludge and their pyrolysis resulted in the enhancedproperties compared to the physical mixture of pyrolized singlecomponents. FIGS. 2A and 2B show the comparison of the volumes of poresmeasured and predicted for the physical mixture of waste oil sludge(WO), sewage sludge (SS) and metal sludge (MS). The generally observedtrend indicates that mixing sludges results in the development of anadditional pore volume. That pore volume, especially mesopores, wasidentified as one of the factors governing the adsorption capacity. FIG.3 shows the dependence of the H₂S removal capacity on the volume ofmesopores. Since the analysis of materials pH and thermodesorptionindicated elemental sulfur as an oxidation product, only mesopores canstore such amount of sulfur as found from H₂S breakthrough capacitytests (up to 30 wt %).

Besides porosity, surface chemistry is also altered during pyrolysis ofthe sludge mixture as compared to the single components. FIG. 4 showsthe comparison of the measured and predicted capacity based on theperformance of the individual components assuming the physical mixture.The huge enhancement found, reaching 100%, is the result of changes inthe composition and the surface distribution of an inorganic phase. Thesludges studied contain iron, copper, nickel, zinc, calcium, chromiumand other metals in significant quantities. Their high temperaturereaction in the presence of carbon phase can lead to uniquespinel/mineral-like components active in the oxidation reactions.

FIG. 5 illustrates an increase in the mass of the sample obtained byhigh temperature pyrolysis. FIG. 5 shows DTG curves in nitrogen forselected adsorbants for initial and H₂S exposed samples (E). Thephenomenon was not observed for the samples pyrolized at lowtemperature. While not intending to be bound by theory, the increase maybe a result of nitride formation. It was found the certain ceramicmaterials, when exposed to nitrogen in the presence of char, are able toform nitrides. Formation of these ceramics can be crucial for catalyticperformance.

Although the best adsorbents are obtained at about 650° C., the synergyis the most predominant at about 950° C. when a mineral like/ceramicphase is formed. Moreover, an increase in the mass of samples undernitrogen at about 600° C. indicates that ceramic components ofadsorbents form nitrides in the presence of carbon. FIG. 6 illustratesDTG curves in nitrogen for selected adsorbants for initial and H₂Sexposed samples (E). Those ceramics must be active in the process of H₂Sadsorbents since an increase in mass significantly decreased afterexposure to hydrogen sulfide and water. The surface of adsorbentstreated at about 950° C. has very low affinity to retain water(hydrophobic). Temperature has also an effect on the density of thefinal products, which varies from about 0.25 at 650° C. to about 0.50 at950° C.

As mentioned above, unique compounds exist as crystallographic phasesand they consist of metals such as calcium, magnesium, alumina, copper,iron, zinc and nonmetals such as oxygen sulfur, carbon and silica. Thelevel of mineralization increases with an increase in the pyrolysistemperature and time. Higher temperature results in formation of twocomponent metal-nonmetal crystallographic compounds with metals at lowoxidation states. FIGS. 7A and 7B show the changes in the X-raydiffraction pattern for samples obtained at different temperatures. FIG.7A illustrates the X-ray diffraction pattern at 650° C. and FIG. 7B isat 950° C.

Advantages of the present invention include the fact that the sorbentsobtained from industrial sludge have five times higher capacity forhydrogen sulfide removal than unmodified carbons. Their capacity iscomparable to that of caustics impregnated carbon used worldwide ashydrogen sulfide adsorbents in sewage treatment plants. Furthermore, thekinetics of the removal process are very fast and no heat is released.Moreover, during adsorption, H₂S reacts with inorganic matter and isoxidized to elemental sulfur. The product is environmentally inert.Importantly, the pH of the spent material is basic, so it can be safelydiscarded. Only small amounts of SO₂ are released. Another advantage ofthe invention is that, since the sorbents are obtained from wastesludge, the significant amount of industrial and municipal waste can berecycled and reused in sewage treatment plants. The sorbents can be alsoused in desulfurization of gaseous fuels (for fuel cell applications)and in hydrothermal vents. The sorbents find another environmentalapplication in removal of mercury from waste water. Furthermore, thereis the possibility of regeneration of spent materials using heating toabout 300° C. to remove elemental sulfur.

EXAMPLE 1

The homogeneous mixtures of waste sludges were prepared as listed inTable 3 and dried at 120° C. The dried samples were then crushed andpyrolized in a horizontal furnace at 950° C. for 30 min. The temperatureramp was 10 degrees/minute. An inert atmosphere was provided by 10ml/min. flow of nitrogen. The yields, ash content and densities ofmaterials are listed in Table 3. TABLE 3 Adsorbents' composition,yields, ash content and densities. Wet Dry Yield compo- Solid compo-(dry Ash γ Sample sition content sition mass) content* [g/cm³] WO WO:23.6 WO: 29 92 0.48 100% 100% SS SS: 100% 24.6 SS: 100% 45 80 0.46 MSMS: 100% 23.4 MS: 100% 47 @ 0.85 WOSS WO: 50% — WO: 49% 34 @ 0.46 SS:50% SS: 51% WOMS WO: 50% — WO: 50% 50 @ 0.47 MS: 50% MS: 50% WOSSMS WO:40% — WO: 46% 41 @ 0.46 SS: 40% SS: 31% MS 10% MS 23%*Determined as mass left at 950° C. after in TA run in air.@ - not determined due to reaction with air during burning

The performance of materials as sorbents for hydrogen sulfide wasevaluated using lab developed breakthrough tests. Adsorbent samples werepacked into a column (length 60 mm, diameter 9 mm, bed volume 6 cm³) andpre-humidified with moist air (relative humidity 80% at 25° C.) for anhour. The amount of adsorbed water was estimated from the increase inthe sample weight after pre-humidification (the sorbents were removedfrom the column and weighted). Moist air containing 0.3% (3,000 ppm) H₂Swas then passed through the column of adsorbent at 1.4 L/min. Thebreakthrough of H₂S was monitored using an Interscan LD-17 H₂Scontinuous monitor system interfaced with a computer data acquisitionprogram. The test was stopped at the breakthrough concentration of 350ppm. The adsorption capacities of each sorbent in terms of grams of H₂Sper gram of material were calculated by integration of the area abovethe breakthrough curves, and from the H₂S concentration in the inletgas, flow rate, breakthrough time, and mass of sorbent. The obtainedresults are collected in Table 4. TABLE 4 H₂S breakthrough capacities,adsorption of water and surface pH before and after H₂S adsorption BrthBth Water capacity capacity adsorbed Sample [mg/g] [mg/cm³] [mg/g] pHpHE WO 109 52 0 9.9 9.4 SS 45 21 26 10.9 10.0 MS 2.8 2.4 0 10.67 10.04WOSS 108 50 11 10.8 9.1 WOMS 86 40 3 9.9 8.8 WOSSMS 121 56 4 10.5 9.4E - after exposure to H₂S

Characterization of pore sizes and adsorption capacity of materialsprepared was accomplished using physical sorption measurement. Theequilibrium adsorption isotherms of N₂ were measured by volumetrictechniques. From the isotherms, the pore size distribution (PSD) wasevaluated using the Density Functional Theory (DFT). The surface areawas calculated using BET approach and micropore volumes usingDubinin-Radushkevich equation (DR). The results are presented in Table5. The symbol “Δ” represents the difference in the specific pore volumebefore and after deposition of sulfur. For all samples but MS anincrease in the volume of mesopores was found as a result of depositionof elemental sulfur and formation of new pores within that deposit. Theexamples of PSDs are presented in FIG. 8. TABLE 5 Parameters of porousstructure S_(BET) V_(mic) [m²/ [cm³/ ΔV_(mic) V_(mes) ΔV_(mes) V_(t)V_(mic)/ Sample g] g] [cm³/g] [cm³/g] [cm³/g] [cm³/g] V_(t) WO 132 0.0500.314 0.364 14 WO-E 96 0.034 −0.16 0.355 0.041 0.389 8 SS 141 0.0580.151 0.209 28 SS-E 121 0.032 −0.26 0.190 0.039 0.222 17 MS 10 0.0020.015 0.017 12 MS-E 4 0.001 −0.01 0.005 −0.010 0.006 17 WOSS 150 0.0610.163 0.224 41 WOSS-E 89 0.030 −0.31 0.258 0.096 0.288 31 WOMS 70 0.0220.144 0.166 13 WOMS-E 60 0.017 −0.05 0.154 0.010 0.171 11 WOSSMS 1440.053 0.267 0.320 20 WOSSMS-E 59 0.022 −0.21 0.183 −0.085 0.205 11WO—waste oil origin;SS—sewage sludge origin;MS—metal sludge origin;E—after exposure to H₂S.

Thermal analysis was carried out to identify the oxidation products andto balance the amount of sulfur deposited on the surface and the resultsare below in Table 6. The peaks between 200-450° C., illustrated in FIG.9, represent the removal of elemental sulfur. TABLE 6 Weight losses invarious temperature ranges and amount of sulfur adsorbed from H₂Sbreakthrough capacity test. Weight loss is corrected for amount adsorbedin H₂S breakthrough test (Bth. Cap.) S Bth Sample 20-150° C. Δ 150-450°C. Δ 450-700° C. Δ 800-1000° C. Δ Total Δ Capacity WO 3.02 0.84 0.05 2.3WO-E 2.31 0 9.20 8.36 1.0 0.95 1.9 0.0 9.31 10.2 SS 2.40 1.15 0.12 4.966.22 SS-E 3.45 1.0 1.15 0 0.03 0 2.7 6.8 4.23 WOSS 3.48 0.21 0.43 2.67WOSS-E 3.15 0 5.85 5.64 0.53 0.1 2.67 0 5.64 10.1 WOMS 0.58 +1.88 +0.802.64 WOMS-E 0.81 0.23 2.56 4.44 +0.59 0.21 2.12 0 4.88 8.08 WOSSMS 1.770.06 0.55 2.83 WOSSMS-E 3.30 1.53 2.34 2.28 0.58 0.03 4.11 1.28 5.1211.4E - after exposure to H₂S.

X-Ray fluorescence was used to evaluate the content of iron, and sulfurafter exhaustion. The results are presented in Table 7. Although thetotal amount is not given the intensities of the peaks in arbitraryunits are related to the amount of specific species. TABLE 7 XRFresults. Sample Fe S(E) WO 139.6 2496.86 SS 8584.02 ND MS 12844.08 NDWOSS 7321.80 ND WOMS 12574.54  732.85 WOSSMS 12173.98 1352.93

EXAMPLE 2

The homogeneous mixtures of waste sludges were prepared as listed inTable 8 and dried at 120° C. The dried samples were then crushed andpyrolized in a horizontal furnace at 650° C. for 30 min. The temperatureramp was 10 degrees/minute. An inert atmosphere was provided by 10ml/min flow of nitrogen. The yields, ash content and densities ofmaterials are listed in Table 8. TABLE 8 Adsorbents' composition, yield,and densities Yield Wet Solid Dry (dry γ Sample composition contentcomposition mass) [g/cm³] WOLT WO: 100% 23.6 WO: 100% 32 0.26 SSLT SS:100% 24.6 SS: 100% 47 0.52 MSLT MS: 100% 23.4 MS: 100% 0.47 WOSSLT WO:50% — WO: 49% 0.36 SS: 50% SS: 51% WOMSLT WO: 50% — WO: 50% 58 0.38 MS:50% MS: 50% WOSSMSLT WO: 40% — WO: 46% 46 0.38 SS: 40% SS: 31% MS 10% MS23%*Determined as mass left at 950° C. after thermol analyses run in air.LT—low temperature, 650° C.

The performance of materials as sorbents for hydrogen sulfide wasevaluated using lab developed breakthrough tests. Adsorbent samples werepacked into a column (length 60 mm, diameter 9 mm, bed volume 6 cm³) andpre-humidified with moist air (relative humidity 80% at 25° C.) for anhour. The amount of adsorbed water was estimated from the increase inthe sample weight after pre-humidification (the sorbents were removedfrom the column and weighted). Moist air containing 0.3% (3,000 ppm) H₂Swas then passed through the column of adsorbent at 1.4 L/min. Thebreakthrough of H₂S was monitored using an Interscan LD-17 H₂Scontinuous monitor system interfaced with a computer data acquisitionprogram. The test was stopped at the breakthrough concentration of 350ppm. The adsorption capacities of each sorbent in terms of grams of H₂Sper gram of material were calculated by integration of the area abovethe breakthrough curves, and from the H₂S concentration in the inletgas, flow rate, breakthrough time, and mass of sorbent. The obtainedresults are collected in Table 9. TABLE 9 H₂S breakthrough capacities,adsorption of water and surface pH before and after H₂S adsorption BthBrth capacity capacity Water adsorbed Sample [mg/g] [mg/cm³] [mg/g] pHpH-E WOLT 315 82 48 9.3 9.3 SSLT 9 5 18 10.9 11.1 MSLT 79 37 0 7.8 7.1WOSSLT 146 53 21 9.2 9.1 WOMSLT 130 49 14 9.8 9.4 WOSSMSLT 73 33 20 9.79.2LT—low temperature, 650° C.;E - after exposure to H₂S.

Characterization of pore sizes and adsorption capacity of materialsprepared was accomplished using physical sorption measurement.Equilibrium adsorption isotherms of N₂ will be measured by volumetrictechniques. From the isotherms the pore size distribution was evaluatedusing the Density Functional Theory (DFT). The surface area wascalculated using BET approach and micropore volumes usingDubinin-Radushkevich equation (DR). The results are presented in Table10. The symbol “Δ” represents the difference in the specific pore volumebefore and after deposition of sulfur. TABLE 10 Parameters of porousstructure S_(BET) V_(mic) V_(mes) [m²/ [cm³/ ΔV_(mic) [cm³/ ΔV_(mes)V_(t) V_(mic)/ Sample g] g] [cm³/g] g] [cm³/g] [cm³/g] V_(t) WOLT 2020.074 0.765 0.839 10 WOLT-E 83 0.032 −0.42 0.434 −0.321 0.517 6 SSLT 920.037 0.113 0.150 25 SSLT-E 79 0.029 −0.008 0.106 −0.007 0.135 27 MSLT34 0.014 0.122 0.136 11 MSLT-E 25 0.011 −0.003 0.160 0.038 0.171 6WOSSLT 154 0.058 0.459 0.517 12 WOSSLT-E 72 0.027 −0.031 0.281 −0.1780.308 10 WOMSLT 92 0.036 0.270 0.306 12 WOMSLT-E 65 0.026 −0.010 0.265−0.005 0.291 9 WOSSMSLT 110 0.042 0.372 0.415 10 WOSSMSLT-E 59 0.023−0.011 0.250 −0.122 0.273 8LT—low temperature, 650° C.;E - after exposure to H₂SThermal analysis was carried out to identify the oxidation products andto balance the amount of sulfur deposited on the surface is listed inTables 11A and 11B, noting two different temperature ranges.

Tables 11A and 11B—Weight losses [in %] in various temperature rangesand amount of sulfur adsorbed from H₂S breakthrough capacity test [in%]. Weight loss is corrected for amount adsorbed in H₂S breakthroughtest (Bth. Cap.); (LT—low temperature, 650° C.; E—after exposure toH₂S). TABLE 11A S brth Sample 20-150° C. Δ 150-450° C. Δ 450-700° C. Δ800-1000° C. Δ Total Δ capacity WOLT 4.70 1.85 1.00 6.69 WOLT-E 7.212.51 34.6 32.75 4.88 3.88 7.28 0.59 39.7 29.6 SSLT 1.86 0.59 0.97 9.18SSLT-E 3.34 1.48 1.40 0.81 1.93 0.96 9.53 0.35 3.6 8.4 WOSSLT 3.56 1.491.04 10.46 WOSSLT-E 5.20 1.64 15.9 14.41 2.87 1.83 12.17 1.71 19.59 13.7

TABLE 11B S brth Sample 20-150° C. Δ 150-400° C. Δ 400-650° C. Δ150-650°C. Total Δ capacity WOLT 4.70 1.71 0.77 WOLT-E 5.42 0.72 23.35 21.643.41 2.64 31.6 31 SSLT 1.86 0.46 0.68 SSLT-E 3.08 1.22 1.03 0.57 1.480.80 1.38 0.9 MSLT 3.66 1.37 0.78 MSLT-E 4.48 0.82 13.3 11.93 2.28 1.515.2 14.3 WOSSLT 1.01 0 2.49 WOSSLT-E 1.16 0.15 6.62 6.62 2.13 0 7.147.7 WOMSLT 3.31 0 0.93 WOMSLT-E 2.86 0 6.13 6.13 2.78 1.85 9.00 12.7WOSSMSLT 1.52 0 3.23 WOSSMSLT-E 4.65 3.13 8.2 8.2 3.16 0 9.20 12.0

EXAMPLE 3

The homogeneous mixtures of waste sludges were prepared as listed inTable 12 and dried at 120° C. The dried samples were then crushed andpyrolyzed in a horizontal furnace at 950° C. for 60 min. The temperatureramp was 10 deg/min. An inert atmosphere was provided by 10 ml/min flowof nitrogen. The yields and densities of the materials are listed inTable 12. TABLE 12 Adsorbents' composition and their densities Wet SolidDry γ Sample composition content composition [g/cm³] WO60 WO: 100% 23.6WO: 100% 0.47 SS60 SS: 100% 24.6 SS: 100% 0.46 MS60 MS: 100% 23.4 MS:100% 0.84 WOSS60 WO: 50% — WO: 49% 0.41 SS: 50% SS: 51% WOMS60 WO: 50% —WO: 50% 0.46 MS: 50% MS: 50% WOSSMS60 WO: 40% — WO: 46% 0.45 SS: 40% SS:31% MS 10% MS 23%

The performance of materials as sorbents for hydrogen sulfide wasevaluated using lab developed breakthrough tests. Adsorbent samples werepacked into a column (length 60 mm, diameter 9 mm, bed volume 6 cm³) andprehumidified with moist air (relative humidity 80% at 25° C.) for anhour. The amount of adsorbed water was estimated from the increase inthe sample weight after pre-humidification (the sorbents were removedfrom the column and weighted). Moist air containing 0.3% (3,000 ppm) H₂Swas then passed through the column of adsorbent at 1.4 L/min. Thebreakthrough of H₂S was monitored using an Interscan LD-17 H₂Scontinuous monitor system interfaced with a computer data acquisitionprogram. The test was stopped at the breakthrough concentration of 350ppm. The adsorption capacities of each sorbent in terms of grams of H₂Sper gram of material were calculated by integration of the area abovethe breakthrough curves, and from the H₂S concentration in the inletgas, flow rate, breakthrough time, and mass of sorbent. The obtainedresults are collected in Table 13. TABLE 13 H₂S breakthrough capacities,adsorption of water and surface pH before and after H₂S adsorption (E -after exposure to H₂S) Brth Bth Water capacity capacity adsorbed Sample[mg/g] [mg/cm³] [mg/g] pH pH-E WO60 61 29 11 10.7 10.2 SS60 78 36 2610.5 9.3 MS60 2 1.7 0 9.8 9.6 WOSS60 78 32 36 11.8 9.8 WOMS60 9.4WOSSMS60 73 33 20 10.7 10.2

EXAMPLE 4

X-ray diffraction measurements were conducted on WO, SS, MS, WOSS andWOSSMS adsorbent samples using standard powder diffraction procedure.Adsorbents were ground with methanol in a small agate mortar. Grindingof the adsorbents by hand ensures particle sizes between 5-10 μm, whichprevents line broadening in diffraction peaks. The mixture wassmear-mounted onto the zero-background quartz window of a Philipsspecimen holder and allow to air dry. Samples were analyzed by Cu K□radiation generated in a Phillips XRG 300 X-ray diffractometer. A quartzstandard slide was run to check for instrument wander and to obtainaccurate location of 2Θ peaks.

In the waste oil based sludge sample heated at 650° C. (WO650) onlymetallic copper was detected as a separate crystallographic phase. See,FIG. 10. In the case of SS650, quartz (SiO₂), cristobalite (SiO₂),truscottite (Ca₁₄Si₂₄)O₅₈(OH)₈2 H₂O), and metallic iron are present.After mixing two components and heating at 650° C., besides quartz,cristobalite and metallic iron and copper, anorthite (CaAl₂Si₂O₈) anddiaspore (AlO(OH)) are detected.

Comparison of the diffraction patterns presented in FIG. 10 clearlyshows the synergetic effect in the chemical composition of materials.New components formed having their origin on addition of silica (comingfrom sewage sludge), and iron and zinc from waste oil sludge. Theseresults indicated formation of new phases with an increase in thepyrolysis temperature and time. FIG. 10 shows the changes in chemistryafter pyrolysis for half an hour at 650° C. while FIGS. 7A and 7Bcompare the sample pyrolyzed at 950° C.

The examples of crystallographic phases found for samples pyrolyzed atvarious conditions are presented in Tables 14 and 15. The headingsindicate the composition of the sample, the temperature it was pyrolyzedat and the duration of the pyrolysis. For example, SS650-0.5 is sewagesludge pyrolyzed at 650° C. for 30 minutes. TABLE 14 Crystallographicphases identified based on XRD analysis WOSS650- WO950- SS650-0.5WO650-0.5 0.5 SS950-0.5 0.5 WOSS950-0.5 Aluminum Aluminum Anorthite AlAl CaAl₂Si₂O₈ Iron, Fe Iron, Fe Iron, Fe Bayerite Al(OH)₃ BorniteBornite Bornite Cu₅FeS₄ Cu₅FeS₄ Cu₅FeS₄ Maghemite Fe₂O₃ Cohenite Fe₃CLawsonite CaAl₂Si₂O₇(OH)₂H₂O Hibonite CaAl₁₂O₁₉ Diaspore AnkeriteAlO(OH) Ca(Fe,Mg)CO₃)₂ Calcite Huntite Vaterite Vaterite magnesiumMg₃Ca(CO₃)₄ CaCO₃ CaCO₃ Sapphirine Sapphirine Sapphirine(Mg₄Al₄)Al₄Si₂O₂₀ (Mg₄Al₄)Al₄Si₂O₂₀ (Mg₄Al₄)Al₄Si₂O₂₀ Spinel SpinelMgAl₂O₄ MgAl₂O₄ Barringerite Zincite Zincite Fe₂P ZnO ZnO WurtiziteWurtzite ZnS ZnS Goethite Ferroxyhite, goethite Lepidicrocite, FeO(OH)FeO(OH) FeO(OH) Almandine Smithsonite Fe₃Al₂(SiO₄)₃ ZnCO₃ Quartz, QuartzQuartz Cristobalite SiO₂ SiO₂ SiO₂

TABLE 15 Crystallographic phases identified based on XRD analysis MS650MS950 WOSSMS650 WOSSMS950 Aluminum Aluminum Al Iron, Fe Iron, Fe Iron FeCopper, Cu Copper, Cu Zinc, Zn Huntite Mg₅Ca(CO₃) Hematite, Fe₂O₃Fersilicite, FeSi Moisanite, SiC Margarite, CaAl(Si₂Al₂)O₁₀(OH)₂Almandine Sphalerite, ZnS Fe₃Al₂(SiO₄)₃ Pyrrhotite, Fe_(1−x)SPyrrhotite, Fe_(1−x)S Pyrrhotite, Fe_(1−x)S Trioilite, FeS Trioilite,FeS Trioilite, FeS Pyrope, Mg₃Al₂(SiO₄)₃ Spinel MgAl₂O₄ ChalocopyriteCuFeS₂ Pyrrohotite Sphalerite Fe₇S₈ ZnS Zhanghengite, CuZn Quartz, SiO₂Quartz, Cristobalite Moganite, SiO₂ SiO₂

Thus, in sewage sludge origin materials obtained at 950° C. suchspinel-like compounds as wurtzite (ZnS), ferroan(Ca₂(Mg,Fe)₅(SiAl)₈O₂₂(OH)₂), chalcocite (Cu_(1.96)S), spinel (MgAl₂O₄),and feroxyhite (FeO(OH)) were found. In waste oil-based materialsbesides metallic iron, bornite (Cu₅FeS₄), hibonite (CaAl₁₂O₁₉), zincite(ZnO), ankerite (Ca(Fe, Mg)(CO₃)₂) are present. In metal sludge basedadsorbent aluminum, metallic iron, copper, zinc, pyrope (Mg₃Al₂(SiO₄)₃₎,perrohotite (Fe₇S₈), Chalocopyrite (CuFeS₂), Triolite (FeS) andFersilicite, (FeSi) exist. Mixing sludges results in synergy enhancingthe catalytic properties which is linked to formation of new entitiessuch as sapphirine (Mg_(3.5)Al₉Si_(1.5)O₂₀), maghemite (Fe₂O₃), cohenite(Fe₃C), lawsonite (CaAl₂Si₂O₇(OH)2H₂O), smithsonite (ZnCO₃), sphalerite(ZnS), and hematite (Fe₂O₃).

The materials obtained at 650° C. differ significantly from thoseobtained at 950° C. In the latter, more double-componentcrystallographic phases (metal-nonmetal) are present with metals atlower oxidation states. The samples pyrolyzed at 650° C. contain morealuminosilicates with calcium, magnesium and iron cations.

EXAMPLE 5

The performance of adsorbents obtained at 650° C. and 950° C. for 0.5hour or 1 hour as H₂S removal media was compared. The results arepresented in Tables 16-18. TABLE 16 H₂S breakthrough capacities, amountof water pre-adsorbed, and pH values for the initial and exhaustedadsorbents. H₂S Brth. H₂S Brth. Water Cap. Cap. adsorbed Sample [mg/g][mg/cm³] [mg/g] pH pH-E WO650-0.5 315 82 48 9.3 9.3 WO950-0.5 109 52 09.9 9.4 WO950-1 62 29 11 10.7 10.2 SS650-0.5 9 5 18 10.9 11.1 SS950-0.542 21 26 10.9 10.0 SS950-1 78 36 26 10.5 9.3 WOSS950-0.5 146 53 21 9.29.1 WOSS950-0.5 108 50 11 10.8 9.1 WOSS950-1 78 32 36 11.8 9.4

TABLE 17 Shift in the pH − ΔpH between initial and exhausted samples,amount of sulfur expected based on the H₂S breakthrough capacity −SBT,weight loss between 150-400° C., □W, and selectivity for oxidation toelemental sulfur, S_(el) S_(BT) ΔW S_(el) Sample ΔpH [%] [%] [%]WO650-0.5 0 30.8 22.52 73 WO950-0.5 0.5 10.7 6.04 56 WO950-1 0.5 6.14.39 72 SS650-0.5 0 0.8 0.15 19 SS950-0.5 0.9 4.1 2.02 47 SS950-1 0.87.7 4.32 56 WOSS650-0.5 0.1 14.2 11.91 83 WOSS950-0.5 1.7 10.6 4.58 42WOSS950-1 2.4 7.7 6.32 82

TABLE 18 Structural parameters calculated from nitrogen adsorptionisotherms S_(BET) V_(mic) V_(mes) V_(t) Sample [m²/g] [cm³/g] [cm³/g][cm³/g] V_(mes)/V_(t) WO650-0.5 202 0.074 0.765 0.839 0.92 WO650-0.5E 830.032 0.434 0.517 0.84 WO950-0.5 132 0.050 0.314 0.364 0.86 WO950-0.5E96 0.054 0.355 0.389 0.91 WO950-1 92 0.037 0.303 0.340 0.89 WO950-1E 640.024 0.275 0.299 0.92 SS650-0.5 92 0.037 0.113 0.150 0.75 SS650-0.5E 790.029 0.106 0.135 0.78 SS950-0.5 141 0.058 0.151 0.209 0.72 SS950-0.5E121 0.032 0.190 0.222 0.85 SS950-1 125 0.049 0.138 0.187 0.74 SS950-1E47 0.018 0.124 0.132 0.94 WOSS650-0.5 154 0.058 0.459 0.517 0.89WOSS650-0.5E 72 0.027 0.281 0.308 0.91 WOSS950-0.5 150 0.061 0.163 0.2240.73 WOSS950-0.5E 89 0.030 0.258 0.288 0.89 WOSS950-1 199 0.075 0.3770.447 0.84 WOSS950-1E 79 0.031 0.269 0.300 0.90

The results demonstrate the possibility of obtaining the valuabledesulfurization catalysts from mixture of waste oil sludge and sewagesludge. Up to 30 wt % hydrogen sulfide can be retained on their surface.The surface properties, such as porosity, selectivity, or catalyticactivity can be modified by changing the pyrolysis conditions. Thecatalytic activity and hydrogen sulfide removal capacity are directlyrelated to the new surface chemistry formed by solid-state reactionsduring pyrolysis. This chemistry can also be controlled to certaindegree by varying the composition of the precursor mixture. As a resultof the synergy between the sludge components new chemistry and porosityis formed which enhances both the physicochemical properties of thematerials and their performance. FIG. 11 shows the comparison of thepredicted (based on the composition and yield of the individualcomponents) and measured volume of mesopores while FIG. 12 compares thepredicted and measured H₂S breakthrough capacities.

EXAMPLE 6

Equilibrium studies for adsorption of acid red and basic fuchsin wereconducted in a series of 100 ml Erlenmeyer flasks at 293 K. Each flaskwas filled with 10 ml of dye solution with concentrations between10-1000 mg/l. After equilibration, the samples were filtrated, analyzedfor their dyes content and the equilibrium adsorption capacity wascalculated. The equilibrium data was fitted to the so-calledLangmuir-Freundlich single solute isotherm. The results are presented inTable 19. The variable q_(m) is the adsorption capacity per unit gram ofadsorbent, K is the Langmuir-type equilibrium constant, and theexponential term n is the heterogeneity parameter of the site energy.TABLE 19 Fitting parameters to Langmuir-Freundlich isotherm q_(m) Kample [mg dye/g] [l/mg] n R² Acid Red1 SS 45.00 0.10 0.44 0.9706 WO46.35 0.14 0.23 0.9757 WOSSO 71.19 0.17 0.75 0.9610 WOSS650 68.40 0.150.74 0.9325 WVA 71.42 0.029 0.76 0.9919 Basic Fuchsin SS 70.36 0.03 0.360.9969 WO 94.21 0.18 0.65 0.9851 WOSS 126.89 0.29 0.59 0.9929 WOSS650105.94 0.15 0.57 0.9804

The adsorption capacity is much higher than that for commercialactivated carbon and it is attributed to the high volume of mesoporesand the presence of mineral-like structures, which can participate inion exchange reactions and precipitation reactions.

EXAMPLE 7

To check the effect of water exposure on the porosity of samples, thematerials were dispersed in water and shake in room temperature for 24hours. After drying the surface area, pore volumes and the average poresizes were determined. The results indicted an increase in the volume ofmesopores are as a result of the reaction of inorganic oxides/salts withwater. The results are presented in Table 20. Δ is the average poresize. TABLE 20 Structural parameters S_(BET) V_(mic) V_(mes) V_(t) ΔSample (m²/g) (cm³/g) (cm³/g) (cm³/g) V_(mic)/V_(t) (Å) SS 950 103 0.0430.100 0.143 0.301 56 SS950-H₂O 100 0.041 0.095 0.136 0.302 55 W950 1280.047 0.363 0.414 0.114 130 WO950-H₂O 109 0.040 0.390 0.431 0.093 158WOSS950 192 0.077 0.279 0.356 0.216 74 WOSS950-H₂O 174 0.068 0.301 0.3690.184 85 WOSS650 108 0.043 0.317 0.356 0.121 132 WOSSO650-H₂O 199 0.0770.253 0.332 0.232 67

EXAMPLE 8

Equilibrium studies for adsorption of copper were conducted in a seriesof 100 ml Erlenmeyer flasks at 20° C. Each flask was filled with 10 mlof copper chloride solution with concentrations between 10-1000 mg/l.After equilibration, the samples were filtrated, analyzed for theircoppers content and the equilibrium adsorption capacity was calculated.The equilibrium data was fitted to the so-called Langmuir-Freundlichsingle solute isotherm. The results are presented in Table 21. Thevariable q_(m) is the adsorption capacity per unit gram of adsorbent, Kis the Langmuir-type equilibrium constant, and the exponential term n isthe heterogeneity parameter of the site energy. The adsorption capacity,especially for samples obtained at 650° C. is much higher than that onactivated carbon. TABLE 21 Fitting parameters of copper (Cu²⁺)adsorption isotherms to Langmuir-Freundlich Equation q_(m) K Sample [mgCu²⁺/g] [l/mg] n R² SS650 63.48 0.009 0.65 0.9985 WO650 74.28 0.025 0.720.9964 WOSS650 69.72 0.018 0.78 0.9978 SS950 34.01 0.001 0.51 0.9970WO950 15.88 0.006 0.92 0.9834 WOSS950 47.08 0.001 0.43 0.9957

EXAMPLE 9

The content of Fe, Ca, Cu, Zn, and Mg was determined in the singlecomponent samples, and based on the composition of the mixed samples,the content of these elements was evaluated. The results are presentedin Table 22. TABLE 22 Cr Sample Fe [%] Ca [%] Mg [%] Cu [%] Zn [%] [ppm]SS650 4.9 4.8 1.3 0.13 0.19 58 SS950 6.1 5.1 1.1 0.17 0.09 90 WO650 3.24.0 11.0 0.20 0.54 140 WO950 3.7 5.1 8.4 0.25 0.51 280 MS950 2.2 14 0.460.77 0.16 6700 WOSS650* 4.0 4.4 6.15 0.16 0.36 99 WOSS950* 4.9 5.1 4.750.21 0.3 185 WOSSMS950* 4.4 6.9 3.89 0.32 0.27 1488*evaluated assuming the same yield of each component (50%).

EXAMPLE 10

Materials

Two industrial sludges, waste oil sludge (WO) and metal sludge (M) fromNewport News Shipyard were mixed with dry tobacco compost, homogenized,dried at 120° C. for 48 hours and then carbonized at 650° C. and 950° C.in nitrogen in a horizontal furnace. The heating rate was 10 deg/minwith a one hour holding time. The weight of the wet industrial sludges(they contain 75% water) was adjusted to have 10% and 50% industrialsludge component based on the dry mass. The names of the adsorbentsobtained, their compositions along with the yield, ash content and bulkdensity are collected in Table 23. Tobacco waste is referred to as TC.

The waste oil sludge was treated with CaCl₂, Na₃PO₄, NaOH and alum.Metal sludge treatment history includes addition of sulfuric acid andsodium hydroxide for pH adjustments, Al₂SO₄ for coagulation, anionic andcationic polymers, sodium bisulfide for chromium reduction, lime andCaCl₂. Thus, besides alkaline or alkaline earth element-containingcompounds and iron, the waste oil sludge also contains 0.4% Cu, 2% Znand between 200 and 1000 ppm of chromium, lead and nickel. In metalsludge there are less than 1% each of cadmium, chromium, copper, lead,manganese, selenium, vanadium and zinc. The content of volatilecompounds in both waste oil sludge and metal sludge reaches 40% theirdry mass, while the content of water in as-received materials is about75%. TABLE 23 Names of the adsorbents, their compositions, pyrolysistemperature, yield, bulk density an ash content Pyrolysis Bulk DryTemper- Yield Density Ash Sample waste composition ature [° C.] [%][g/cm³] [%] CTCA TC: 100% 650 52 0.63 67 CTCB TC: 100% 950 51 0.52 76CWOB WO: 100% 950 30 0.48 92 CMB M: 100% 950 47 0.58 ND CTCWO-1A TC 90%;WO 10% 650 52 0.42 72 CTCWO-2A TC 50%; WO 50% 650 53 0.41 67 CTCWO-1B TC90%; WO10% 950 45 0.40 78 CTCWO-2B TC: 50%; WO 50% 950 38 0.40 86CTCM-1A TC 90%; M 10% 650 0.55 63 CTCM-2A TC 50%; M 50% 650 65 0.52 86CTCM-1B TC 90%; M 10% 950 0.58 95 CTCM-2B TC 50%; M 50% 950 57 0.30 96Evaluation of H₂S Sorption Capacity

A custom-designed dynamic test was used to evaluate the performance ofadsorbents for H₂S adsorption from gas streams as described above.Adsorbent samples were ground (1-2 mm particle size) and packed into aglass column (length 370 mm, internal diameter 9 mm, bed volume 6 cm³),and pre-humidified with moist air (relative humidity 80% at 25° C.) forone hour. The amount of water adsorbed was estimated from an increase inthe sample weight. Moist air (relative humidity 80% at 25° C.)containing 0.3% (3,000 ppm) of H₂S was passed through the column ofadsorbent at 0.5 L/min. The flow rate was controlled using Cole Parmerflow meters. The breakthrough of H₂S was monitored using MultiRaephotoionization sensor. The test was stopped at the breakthroughconcentration of 100 ppm. The adsorption capacities of each adsorbent interms of mg of hydrogen sulfide per g of adsorbent were calculated byintegration of the area above the breakthrough curves, and from the H₂Sconcentration in the inlet gas, flow rate, breakthrough time, and massof sorbent. For each sample the test was repeated at least twice.Besides H₂S the content of SO₂ in the outlet gas was also monitoredusing MultiRae photoionization sensor. The adsorbents exhausted afterH₂S adsorption are designated by adding an additional letter E to theirnames.

Characterization of Pore Structure of Adsorbents

On the materials obtained sorption of nitrogen at its boiling point wascarried out using ASAP 2010 (Micromeritics). Before the experiments, thesamples were outgassed at 120° C. to constant vacuum (10-4 torr). Fromthe isotherms, the surface areas (BET method), total pore volumes,V_(t), (from the last point of isotherm at relative pressure equal to0.99), volumes of micropores, V_(mic) (DR), mesopore volume V_(mes),total pore volume, V_(t), along with pore size distributions werecalculated (DFT).

pH

The pH of a carbonaceous sample suspension provides information aboutthe acidity and basicity of the surface. A sample of 0.4 g of dry carbonpowder was added to 20 mL of distilled water and the suspension wasstirred overnight to reach equilibrium. Then the pH of suspension wasmeasured.

Thermal Analysis

Thermal analysis was carried out using TA Instrument Thermal Analyzer.The instrument settings were: heating rate 10° C./min and a nitrogenatmosphere with 100 mL/min flow rate. For each measurement about 25 mgof a ground adsorbent sample were used. For analysis of the results thederivative thermogravimetric curves (DTG curves) are used. Ash contentwas determined from the residue left at 800° C. after heating thesamples in air.

Elemental Analysis

Metal content in the adsorbents was determined using ICP in LSL labs,Syracuse, N.Y.

XRD

X-ray diffraction measurements were conducted using standard powderdiffraction procedure. Adsorbents were ground with methanol in a smallagate mortar. Grinding of the adsorbents by hand ensures particle sizesbetween 5-10 μm, which prevents line broadening in diffraction peaks.The mixture was smear-mounted onto the zero-background quartz window ofa Phillips specimen holder and allow to air dry. Samples were analyzedby Cu K_(α) radiation generated in a Phillips XRG 300 X-raydiffractometer. A quartz standard slide was run to check for instrumentwander and to obtain accurate location of 20 peaks.

The H₂S breakthrough curves are presented in FIG. 13 and 14. As seenbased on the steep rise in the breakthrough curves all tobacco basedmaterials have short diffusion zone and almost immediately after H₂S isdetected in the outlet gas, the adsorbents stop to work allowing thechallenge gas to pass chemically undisturbed through the bed. No SO₂concentration was detected which indicates that all H₂S is converted tosulfur. In the case of metal and oil sludge derived materials smallconcentrations of sulfur dioxide, up to few ppm were measured at thesame time when hydrogen sulfide appeared in the outlet gas. Even aftermixing 50% tobacco waste and 50% waste oil, the kinetics of hydrogensulfide retention characteristic to tobacco were still predominant sincethe shape of the slope of the curve does not resemble the one obtainedfor waste oil derived adsorbent.

The results of the H₂S breakthrough capacity measurements are summarizedin Table 24 where besides the capacity expressed unit mass per gram ofthe adsorbents and per unit volume of the bed, the amount of wateradsorbed during the prehumidification and the pH of the surface beforeand after adsorption process are reported.

As seen from Table 24, the highest capacity is found for tobacco wasteoil sludge compositions pyrolyzed at 950° C. Although higher content ofoil sludge is beneficial for the performance, even only 10% waste oilsludge increases the performance about 100% compared to pure tobaccowaste based material. For CTC. material the high temperature ofpyrolysis also significantly enhances the capacity. The results suggestthe predominant influence of the tobacco waste on the performance sincethe waste oil sludge derived materials were reported to have bestcapacity at low temperature. In fact comparison of the capacity obtainedfor both tobacco and waste oils sludge based materials obtained at 950°C. clearly shows the synergetic effect; the capacity obtained for themixture is much higher than for either one of its components. TABLE 24H₂S breakthrough capacity, amount of water adsorbed and the pH values ofadsorbent surfaces. H₂S breakthrough water capacity adsorbed pH Sample[mg/g] [mg/cm³] [mg/g] initial exhausted CWOB 40.2 21.1 11 10.7 10.2 CMB5.0 2.9 0 11.2 11.2 CTC-A 6.6 4.2 51.8 11.2 10.7 CTC-B 23.1 12.1 38.211.3 11.3 CTCWO-1A 16.1 6.7 45.4 10.6 9.6 CTCWO-2A 0.9 0.4 82.0 9.2 9.2CTCWO-1B 42.6 17.8 35.4 10.0 9.8 CTCWO-2B 90.2 36.4 43.3 10.3 9.3CTCM-1A 13.0 7.2 29.6 10.6 10.5 CTCM-2A 22.5 11.7 11.2 9.4 9.3 CTCM-1B23.1 13.5 21.5 11.2 11.1 CTCM-2B 18.9 5.7 10.8 10.8 10.6

As seen from Table 24, the highest capacity is found for tobacco wasteoil sludge mixtures pyrolyzed at 950° C. Although higher content of oilsludge is beneficial for the performance, even only 10% waste oil sludgeincreases the performance about 100% compared to pure tobacco wastebased material. For CTC. material, the high temperature of pyrolysisalso significantly enhances the capacity. These results suggest thepredominant influence of the tobacco waste on the performance since thewaste oil sludge derived materials were reported to have best capacityat low temperature. In fact comparison of the capacity obtained for bothtobacco and waste oils sludge-based materials obtained at 950° C.clearly shows the synergetic effect; the capacity obtained for themixture is much higher than for either one of its components.

Pyrolysis of waste oil sludge/tobacco mixture at 650° C. with a highcontent of waste oil sludge component has a detrimental effect on thecapacity. Although on the surface of this sample the high amount ofwater is adsorbed, the capacity is negligible. Since the materials fromwaste oil sludge pyrolized at 650° C. had a very high capacity (reaching30% wt.), the tobacco component hinders the capacity when lowtemperature treatment is applied. On the other hand, when metal sludgeis used and mixture is pyrolyzed at low temperature, the capacity isenhanced compared to pure tobacco or pure metal sludge. Pyrolyzing thosetwo mixtures at high temperature enhances capacity for low sludgecontent indicating once again the importance of the tobacco phase forhydrogen sulfide removal on composite adsorbents.

Taking into account variations in the behavior of the samples withintheir pyrolysis temperature, the relationship between the amount ofwater preadsorbed and the H₂S breakthrough capacity was analyzed. Asseen from FIG. 15, for the samples pyrolyzed at low temperature have adetrimental effect on the H₂S breakthrough capacity. This may be linkedto the low degree of mineralization and reactivity of the surface. It islikely that exposure to water causes its reaction with metal oxides andformation of hydroxides, which was observed previously. If the smallpores are present, those hydroxides may block their entrances and thusdecrease the available space for H₂S adsorption and sulfur storage. Thisproblem is readdressed below were the porosity is discussed.

In the case of samples pyrolyzed at 950° C., water apparently enhancesthe capacity. This might be linked to its physical retention on thesurface and formation of water film, in which the basic pH exists. Thisenables high concentration of HS⁻ ions and thus their oxidation toelemental sulfur.

All samples have basic pH, which helps with in hydrogen sulfide removal.The lowest pH is found for the CTCWO-2A sample, which has also the verylow H₂S removal capacity. That pH is much lower than the pH of itscomponents. The reason for this might be either in oxidation of thecarbon phase or specific chemistry formed as a result of synergeticeffect between the composite components.

Checking the synergetic effect on the H₂S breakthrough capacity, themeasured values were compared to those calculated assuming the physicalmixtures of the components, and taking into account their yields. Theresults presented in FIG. 16. While in the case of metal sludge onlyslight enhancement in the capacity is observed as a result of mixing,for the waste oil sludge/tobacco composites a significant synergeticeffect is found with four fold increase in the capacity for CTCWO-2B.

That synergetic effect might be the result of either new catalyticphases formed when the materials are mixed and exposed to hightemperature, formation of new pores enhancing physical adsorption andstorage of oxidation products, an increased dispersion of catalyticphase, or more likely, the combination of all of these factors.

Using X-ray diffraction one may see both, the changes in the degree ofcrystallinity of the adsorbents and the formation of new phases as aresult of solid state reaction. FIG. 17 shows the comparison of XRDpatterns for CTC adsorbents obtained at 650 and 950° C. As seen from theanalysis of the ash content (Table 23) all adsorbents, even thosederived from only tobacco waste have the majority of the inorganicphase. In the case of CTCA only quartz, and magnesian of ferrosilite((Fe,Mg)SiO₃) are identified. Heating at 950° C. results in formation ofmore crystalline phases identified as bayerite (Al(OH)₃), orderedanorthite (CaAl₂Si₂O₈),anthophyllite ((Mg, Fe)₇Si₈O₂₂(OH)₂), andbarrigerite (Fe₂P). Some of these minerals such as barrigerite, werealso identfied in sewage sludge derived materials in which enhanced H₂Sadsorption was found. Magnesium, calcium and iron from these mineralscan contribute to catalytic oxidation of hydrogen sulfide to sulfur. Inthe case of CWOB metallic iron, bornite (Cu₅FeS₄), hibonite (CaAl₁₂O₁₉),zincite (ZnO) and ankerite (Ca(Fe Mg)(CO₃)₂) are detected (FIG. 18).Heating metal sludge to 950° C. resulted in formation of numerouscrystalline phases (multipeak pattern) from which pyrrohotite(Fe_(1-x)S), troilite (FeS), pyrope (Mg₃Al₂(SiO₄)₃), and metalliccopper, zinc and iron have high probability to exist.

A multipeak pattern is also observed for the mixtures of tobacco withmetal sludge of various compositions and pyrolyzed at two differenttemperatures. Comparison of FIGS. 17, 18 and 19 clearly shows that newphases are detected. Examples of these new phases for CTCM-1A are spinel(MgAl₂O₄), margarite (CaAl₂(Si₂Al₂)O₁₀(OH)₂), malachite (Cu₂CO₃(OH)₂,calcite (CaCO₃), cordierite (Mg₂Al₄Si₅O₁₈), pigeonite (Fe,Mg,Ca)SiO₃),corundum (Al₂O₃), tenorite (CuO), magnesioferrite (MgFe₂O₄), moissanite(SiC) and metallic iron. By pyrolyzing at 950° C., the mixturecontaining more metal sludge derived phase results in even more complexchemistry with predominant structures of mixed calcium iron andmagnesium silicates and aluminosilicates. Some of them, as ferrocilite,anorthite were present in CTC-A. Examples are fosterite (Mg₂SiO₄),huntite (Mg₃Ca(CO₃)₄), aragonite (CaCO₃), wollastonite (CaSiO₃),dolomite (CaMg(CO₃)₂, cohenite, (Fe₃C) fersilicite (FeSi), covelite(CuS), bornite (Cu₅FeS₄), grunerite (Fe₇Si₈O₂₂(OH)₂), hardystonite(Ca₂ZnSi₂O₇) or akermanite (Ca₂MgSi₂O₇). In this case, compared to thesample pyrolized at 650° C., more carbonates are present, likely theresult of gasification of carbon, less aluminum is involved incrystalline phase, and more two element-compounds appear.

Very complex and different form parent compound structure is obtainedfor CTCWO-2B (FIG. 19). In this case, besides significant amount ofquartz, over 50 new compounds were detected. They are mainlyaluminoslicate with magnesium, calcium, iron, sodium, copper and lead.Examples include: sodian of anorthite ((Ca, Na) (Al, Si)₂Si₂O₈),forsterite (Mg₂SiO₄), albite (CaAl₂Si₂O₈), richterite(KNaCaMg₅Si₈O₂₂(OH)₂), renhahnite (Ca₃(Si₃O₈(OH)₂), Dahlite(Ca_(9.35)Na_(1.07)(PO₄)_(5.46)CO₃), rockbridgeite (Fe₅ (PO₄)₃(OH)₅).

Although surface chemistry can play a crucial role in the process ofhydrogen sulfide oxidation on the surface of materials studied, itseffects cannot be discussed in isolation from the description of porousstructure. The nitrogen adsorption isotherms are collected in FIGS. 20and 21. Their shapes and nitrogen uptakes indicate differences in thesizes and volume of pores. While tobacco derived adsorbents are bothvery microporous, addition of waste oil sludge and metals sludgecomponent contributes to the development of mesoporosity. The structuralparameters calculated from nitrogen adsorption isotherms are collectedin Table 25. Either waste oil sludge or metal sludge addition increasethe surface areas of samples obtained at 950° C. in spite of the factthat the surface areas of both components pysolyzed separately are muchsmaller. This indicates the beneficial synergetic effect. Thatdevelopment of porosity can be caused by gasification of carbon phase byalkaline earth metals present in the sludges, which can be considered asself-activation. Adding more waste oil sludge increases surface area,volume of micropores and volume of mesopores. Although the latter arepresent in much higher volume in the CWOB adsorbent, the new volume ofmicropores is the result of activation during pyrolysis. On the otherhand, addition of metal sludge, even in only small quantity seems to bemost beneficial for tobacco/metal sludge mixtures. These materials havea new volume of mesopores formed, which do not exist in either tobaccoor metal sludge only based materials. Gasification can be importanthere. Much more alkaline earth metals than in waste oil sludge results(Table 26) in formation of larger pores in the carbonaceous deposit. Itis interesting that the smallest surface area and pore volume areobtained for metal sludge tobacco mixture with 50/50 ratio ofcomposition pyrolyzed at 650° C. This is consistent with this sample lowcapacity for hydrogen sulfide removal. Since both tobacco derivedsamples have almost identical structural parameters the differences intheir performance as hydrogen sulfide adsorbents must be attributed todifferences in surface chemistry mentioned above. TABLE 25 Structuralparameters calculated from nitrogen adsorption S_(BET) V_(mic) V_(meso)V_(t) D_(BJH) D_(DA) E_(o) Sample [m²/g] [cm³/g] [m²/g] [cm³/g]V_(mic)/V_(t) [Å] [Å] [kJ/mol] CTCA 73 0.037 0.016 0.053 0.698 69 1525.06 CTCAE 0 0 0 0 0 0 0 0 CTCB 78 0.039 0.020 0.059 0.661 41 16 21.82CTCB-E 42 0.017 0.039 0.056 0.304 44 17 19.28 CTCWO-1A 71 0.041 0.0510.092 0.446 95 16 23.80 CTCWO-1AE 33 0.014 0.088 0.102 0.137 100 1717.62 CTCWO-2A 35 0.015 0.165 0.180 0.083 123 21 10.09 CTCWO-2AE 130.009 0.127 0.136 0.066 144 21 9.61 CTCWO-1B 120 0.055 0.096 0.151 0.36456 16 20.65 CTCWO-1BE 37 0.019 0.072 0.091 0.209 68 17 17.55 CTCWO-2B162 0.069 0.180 0.249 0.277 61 17 20.01 CTCWO-2BE 59 0.026 0.163 0.1890.138 85 18 15.45 CTCM-1A 77 0.035 0.071 0.106 0.330 63 15 23.94CTCM-1AE 8 0.006 0.047 0.053 0.113 138 17 18.79 CTCM-2A 74 0.031 0.1440.175 0.177 79 17 18.67 CTCM-2AE 24 0.013 0.115 0.128 0.102 124 18 16.36CTCM-1B 96 0.043 0.113 0.156 0.276 62 16 20.53 CTCM-1BE 46 0.018 0.0970.115 0.157 99 18 15.62 CTCM-2B 59 0.031 0.061 0.092 0.337 82 16 20.19CTCM-2BE 49 0.022 0.109 0.131 0.168 107 18 16.67

After H₂S removal the surface area and volumes of microporessignificantly decrease. For the majority of samples, but CTC-BE,CTCWO-1AE and CTCM-2BE the volume of mesopores increases. Thisphenomenon was observed before and was attributed to formation of newpores within either sulfur deposit in large pores, if capacity was high,or/and formation of hydroxides on the surface as a result of exposure towater during prehumidification. Although in the case of CTCM-2BE onlysmall amount of water was adsorbed with relatively high amount of H₂S,taking into account the small surface area of the samples, asignificant, almost 100% increase in the volume of mesopores can beattributed to that sulfur deposit. The surface in large pores of thematerials must be active since extensive gasification helped in highdispersion on the catalysts on the surface. For CTCWO-1AE, that increasecan be attributed to the formation of hydroxides, since the surface isactive and large amounts of water are adsorbed, and also to sulfurdeposit. These hydroxides can totally block the porosity in the carbondeposit when more sludge derived phase is present and sample is exposedto moisture from the atmosphere. This likely happens in the case ofCTCWO-2A, which was totally inactive in the process of H₂S adsorption,contrary to only waste oil sludge based sample whose capacity was foundsignificant previously and it was attributed to the high volume ofmesopores, which, owing to their large sizes, cannot be blocked byhydroxides. As seen from Table 25 the average pore sizes calculatedusing Dubinin-Astakhov method are related to the values of thecharacteristic energy of adsorption, which is the highest for CTC-A,CTCWO-1A, and CTCM-1A. These materials are obtained at low temperatureso they can be considered as chars or “underactivated” carbons. TABLE 26Content of catalytic metals Sample Fe [%] Ca [%] Mg [%] Cu [%] Zn[%] Cr[ppm] CWOB 3.7 5.1 8.4 0.25 0.51 280 CMB 22 14 0.46 0.77 0.16 6700 CTCB1.45 × 0.0115 0.00255 1.55 × 2 × ND 10 − 4 10⁻⁵ 10⁻⁵

Details about the differences in the porosity of our samples arepresented in FIGS. 22, 23A & B and 24A & B as pore size distributions.For all samples on the distributions two regions can be seen. Oneconsists of micropores which are much more heterogeneous in their sizesfor CTC. and CTWO series of samples than for CTCM. On the other hand,the heterogeneity of mesopores is much greater for the latter group ofsamples. After H₂S adsorption the smallest pores are not seen anymoreindicating that sulfur is deposited either there, or at their entrances,and the new pores appears, especially with the range of sizes between50-200 Å. In same cases it happens with the expense of macropores. Thisshows importance of large porosity with catalytically active surface tothe process of hydrogen sulfide oxidation. If only physical adsorptionwere predominant those pores would not play any role and would have anegative effect on the performance of materials based on the unit volumeof the bed. Thus in the case of this groups of materials very lightadsorbents can be used which may increase the cost effectiveness of theremoval process.

The synergetic effect of the porosity development in our materials ispresented in FIGS. 25 and 26 where the measured volumes of micro andmesopores are compared to those calculated assuming the physical mixtureof the components and taking into account the yield of materials. Asdissussed above, the synergetic effects of the sludge components onactivation of the final products is clearly seen with the mostpronounced effects of waste oil sludge on the volume of micropores andmetal sludge—on the volume of mesopores.

To check the role of porosity for H₂S adsorption, the dependence of thecapacity on the volume of pores was analyzed. The results are presentedin FIG. 27. As seen, a good relationship is found for the volume ofmicropores. They have they origin likely in the tobacco derived carbonphase thus this component of the H₂S adsorption process has to havesimilar mechanism on all tobacco containing samples. Linear trend isalso noticed for the volume of mesopores but only for materials obtainedat 950° C. As it was shown above, water has a detrimental effect on thechemistry of low temperature pyrolyzed samples, thus the linear trend inhis case is not expected. The linear relationship between the capacityand volume of mesopores indicates the activity of large pores in theprocess of hydrogen sulfide catalytic oxidation.

The comparison of DTG curves before and after adsorption of hydrogensulfide is presented in FIGS. 28, 29, and 30. The peaks on the curvesrepresent weight loss due to the decomposition/desorption of surfacespecies. For some initial samples as CTCB, CTCM-1A, CTCM-1B an increasein weight (negative peaks) is observed between 150 and 400° C. andbetween 600 and 800° C. The latter negative peak is also found forCTCWO-2B. This strange behavior was noticed previously for some metalsludge, waste oil sludge and even sewage sludge-based adsorbents. Sinceonly nitrogen was present formation of nitrides was given as the onlyplausible explanation. After H₂S adsorption a negative peak is presentonly at high temperature range for CTCM-2BE. For other samples it iscompensated by weight loss caused by removal of deposited sulfur between200-400° C. Although this weight loss/peak intensity should beproportional to the amount of hydrogen sulfide deposited on the surfacein the case of material pyrolyzed at 650° C. addition to the weight lossoccurs as a result of dehydroxylation of surface at temperature smallerthan 600° C. The hydroxides were formed when samples were exposed towater during prehumidification and H₂S adsorption.

Pyrolysis of waste tobacco compost and industrial sludges from heavyindustries leads to the development of effective catalyst fordesulfurization of air. An important role of carbonaceous phase derivedfrom waste tobacco is in its relatively high carbon content. That carboncontributes to the development of porosity in both, micro and mesoporeranges. This happens via self-activation of carbon material by alkalineearth metals and water released from the decomposition of inorganicmatter during heat treatment. As a result of solid state reactions athigh temperature new catalytic species are formed on the surface ofadsorbent as a result of synergy between the components of sludges.Location of these species in mesopores is beneficial for thedesulfurization process. The surface of those pores retain water filmwhere hydrogen sulfide can dissociate in the basic environment, Sulfurformed in oxidation reaction can be stored there in large quantitywithout rapid deactivation of the catalytic centers by stericalhindrances. High temperature of pyrolysis is beneficial for theadsorbents due to the enhanced activation of carbonaceous phase andchemical stabilization of inorganic phase. Samples obtained at lowtemperature are sensitive to water, which deactivates their catalyticcenters.

The present invention is not to be limited in scope by the specificembodiments described herein. Indeed, various modifications of theinvention in addition to those described herein will become apparent tothose skilled in the art from the foregoing description and theaccompanying figures. Such modifications are intended to fall within thescope of the appended claims.

It is further to be understood that all values are approximate, and areprovided for description.

Patents, patent applications, publications, product descriptions, andprotocols are cited throughout this application, the disclosures ofwhich are expressly incorporated herein by reference in their entiretiesfor all purposes.

1. An adsorbent derived from one of compost or compost materials andsludge comprising: a) 20-30% porous carbon with incorporated organicnitrogen species; and b) 70-80% inorganic matter, wherein the sludge isa at least one of industrial or municipal sludge.
 2. The adsorbent ofclaim 1, wherein the inorganic matter includes highly dispersedcatalytic oxides.
 3. The adsorbent of claim 2, wherein the catalyticoxides are one or more of copper oxide, zinc oxide, iron oxide, calciumoxide, silica and alumina.
 4. The adsorbent of claim 1, wherein thenitrogen species comprises amine or pyridine groups.
 5. The adsorbent ofclaim 1, wherein the surface area of the adsorbent is 100-500 m2/g. 6.The adsorbent of claim 5, wherein the surface area of the adsorbent is100-200 m2/g.
 7. The adsorbent of claim 1, wherein the adsorbentcontains micropores and the volume of the micropores are at least 0.03cm 3/g.
 8. The adsorbent of claim 1, wherein the pH of the adsorbent isgreater than
 10. 9. The adsorbent of claim 1, wherein the pH of theadsorbent is between 7 and
 10. 10. The adsorbent of claim 1, wherein thepH of the adsorbent is between 4 and
 7. 11. A method of making anadsorbent which comprises the steps of: a) composting compost materials;b) thermally drying dewatered sewage sludge to form granulated organicfertilizer; c) mixing the organic fertilizer and the compost; and b)pyrolyzing the mixture at temperatures between 600° C. and 1000° C. 12.The method of claim 11, wherein the heating rate is between 5 and 10°C./minute and the hold time is between 60 and 90 minutes.
 13. The methodof claim 11, wherein the temperature of pyrolysis is between 800 and1000° C.
 14. The method of claim 13, wherein the temperature ofpyrolysis is between 900 and 1000° C.
 15. The method of claim 11,wherein the temperature of pyrolysis is between 600 and 900° C. and theadsorbent is further treated with 15-20% HCl.
 16. The method of claim15, wherein the temperature of pyrolysis is between 800 and 900° C. 17.The method of claim 11, further comprising the step of treating themixture with between about 5 and about 30 wt % mineral oil, and whereinthe mineral oil is selected from light mineral oil, heavy mineral oil,natural mineral oil, synthetic mineral oil, spent motor oil, andcombinations thereof.
 18. The process of removing acidic gases from wetair streams comprising putting an adsorbent comprising 20-30% porouscarbon with incorporated organic nitrogen species and 70-80% inorganicmatter derived from sewage sludge in contact with the wet air stream andallowing the adsorbent to adsorb the acidic gases.
 19. The process ofclaim 18, wherein the acidic gases are one or more of hydrogen sulfide,sulfur dioxide, hydrogen cyanide, and nitrogen dioxide.
 20. The processof claim 18, wherein the acidic gas is hydrogen sulfide which reactswith inorganic matter to be oxidized to sulfur dioxide or elementalsulfur and salt forms thereof.
 21. The process of claim 18, wherein thewet air stream is effluent from a sewage treatment plant, gaseous fuel,or gases from hydrothermal vents.
 22. The process of removing acidicgases from wet air streams comprising: composting compost materials;forming an adsorbent by thermally drying dewatered sewage sludge to formgranulated organic fertilizer; mixing the compost with the organicfertilizer; and pyrolyzing said mixture at temperatures between600-1000° C., putting said adsorbent in contact with the wet air stream,and allowing the adsorbent to adsorb the acidic gases.
 23. The processof claim 22, wherein the acidic gases are one or more of hydrogensulfide, sulfur dioxide, hydrogen cyanide, and nitrogen dioxide.
 24. Theprocess of claim 22, wherein the temperature of pyrolysis is between 800and 1000° C.
 25. The process of claim 24, wherein the temperature ofpyrolysis is between 900 and 1000° C.
 26. The process of claim 22,wherein the temperature of pyrolysis is between 600 and 900° C. and theadsorbent is further treated with 15-20% HCl.
 27. The process of claim26, wherein the temperature of pyrolysis is between 800 and 900° C. 28.The process of claim 22, wherein the adsorbent may be regenerated byheating to 300-500° C. to remove elemental sulfur and sulfur dioxide.29. A method for producing an adsorbent, comprising the steps of:combining a first sludge and at least one of a second sludge and acompost material to form a mixture; thermally drying the mixture;pyrolizing the mixture at a temperature between about 600° C. and 1,100°C.; and forming at least one of wurtzite, ferroan, chalcocite, spinel,feroxyhite, bornite, hibonite, zincite, ankerite, pyrope, perrohotite,chalocopyrite, triolite, fersilicite, sapphirine, maghemite, cohenite,lawsonite, smithsonite, sphalerite, goethite, huntite, anorthite,diaspore, vaterite, lepidirocite, bayerite, moghemite, pyrohotite,hematite, sphalerite, almandine, and hematite during the pyrolizingstep.
 30. The method of claim 29, wherein the compost material is atleast one of tobacco waste, waste paper and wood char, or a combinationthereof, wherein the first sludge is a municipal sludge or an industrialsludge, and wherein the second sludge is a municipal sludge or anindustrial sludge and different from the first sludge.